Ammonium Chloride → (R)-3-(2-aminophenylthio)-2-(benzyloxycarbonylamino)-3-methylbutanoic acid

HRID 1055416Notes

Reaction equation

HRID 1055416 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([C:16]([CH3:28])([S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=1[N+:25]([O-])=O)[CH3:17])[C:13]([OH:15])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH4+].[Cl-]>CO.[Zn]>[NH2:25][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][C:19]=1[S:18][C:16]([CH3:28])([CH3:17])[C@H:12]([NH:11][C:9]([O:8][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:10])[C:13]([OH:15])=[O:14]

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 90037688(R)-2-(benzyloxycarbonylamino)-3-methyl-3-(2-nitrophenylthio)butanoic acid

Product 1

HCID 90037504(R)-3-(2-aminophenylthio)-2-(benzyloxycarbonylamino)-3-methylbutanoic acidYield 100%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 887MethanolSolvent

Procedure

A mixture of (R)-2-(benzyloxycarbonylamino)-3-methyl-3-(2-nitrophenylthio)butanoic acid (18.3 g, 45.2 mmol, Eq: 1.00), NH4Cl (4.84 g, 90.5 mmol, Eq: 2) and Zn (45.9 g, 701 mmol, Eq: 15.5) in MeOH (500 mL) was heated at reflux for 6 h and the mixture was filtered through Celite. The filter cake was washed with hot MeOH. The filtrate was concentrated, the residue was tritrurated with H2O, 1:3 Et2O/Hexane and azeotroped with toluene. The resulting material was dried under vacuum to give (R)-3-(2-aminophenylthio)-2-(benzyloxycarbonylamino)-3-methylbutanoic acid (16.9 g, 100%) which was used without purification.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 6 h
  3. filtrationthe mixture was filtered through Celite
  4. washThe filter cake was washed with hot MeOH
  5. concentrationThe filtrate was concentrated
  6. customazeotroped with toluene
  7. customThe resulting material was dried under vacuum

Sources & evidence

ORD record
ord-91a34fe137ee4ca89fc36a06108ab97a
Source dataset
uspto-grants-2016_07
Patent number
US09394263B2

Reaction notes

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